EP0493721B1 - Styrene derivatives - Google Patents

Styrene derivatives Download PDF

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Publication number
EP0493721B1
EP0493721B1 EP91121314A EP91121314A EP0493721B1 EP 0493721 B1 EP0493721 B1 EP 0493721B1 EP 91121314 A EP91121314 A EP 91121314A EP 91121314 A EP91121314 A EP 91121314A EP 0493721 B1 EP0493721 B1 EP 0493721B1
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Prior art keywords
formula
halogen
weight
compounds
hydrogen
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German (de)
French (fr)
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EP0493721A1 (en
Inventor
Bernd Dr. Schaefer
Lothar Dr. Rueb
Peter Dr. Schaefer
Karl-Otto Dr. Westphalen
Matthias Dr. Gerber
Helmut Dr. Walter
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BASF SE
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BASF SE
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D207/00—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom
    • C07D207/02—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom with only hydrogen or carbon atoms directly attached to the ring nitrogen atom
    • C07D207/44—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having three double bonds between ring members or between ring members and non-ring members
    • C07D207/444—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having three double bonds between ring members or between ring members and non-ring members having two doubly-bound oxygen atoms directly attached in positions 2 and 5
    • C07D207/448—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having three double bonds between ring members or between ring members and non-ring members having two doubly-bound oxygen atoms directly attached in positions 2 and 5 with only hydrogen atoms or radicals containing only hydrogen and carbon atoms directly attached to other ring carbon atoms, e.g. maleimide
    • C07D207/452—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having three double bonds between ring members or between ring members and non-ring members having two doubly-bound oxygen atoms directly attached in positions 2 and 5 with only hydrogen atoms or radicals containing only hydrogen and carbon atoms directly attached to other ring carbon atoms, e.g. maleimide with hydrocarbon radicals, substituted by hetero atoms, directly attached to the ring nitrogen atom
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D207/00—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom
    • C07D207/02—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom with only hydrogen or carbon atoms directly attached to the ring nitrogen atom
    • C07D207/30—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having two double bonds between ring members or between ring members and non-ring members
    • C07D207/34—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having two double bonds between ring members or between ring members and non-ring members with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
    • C07D207/36—Oxygen or sulfur atoms
    • C07D207/40—2,5-Pyrrolidine-diones
    • C07D207/404—2,5-Pyrrolidine-diones with only hydrogen atoms or radicals containing only hydrogen and carbon atoms directly attached to other ring carbon atoms, e.g. succinimide
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N37/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom having three bonds to hetero atoms with at the most two bonds to halogen, e.g. carboxylic acids
    • A01N37/18—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom having three bonds to hetero atoms with at the most two bonds to halogen, e.g. carboxylic acids containing the group —CO—N<, e.g. carboxylic acid amides or imides; Thio analogues thereof
    • A01N37/32—Cyclic imides of polybasic carboxylic acids or thio analogues thereof
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N37/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom having three bonds to hetero atoms with at the most two bonds to halogen, e.g. carboxylic acids
    • A01N37/44—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom having three bonds to hetero atoms with at the most two bonds to halogen, e.g. carboxylic acids containing at least one carboxylic group or a thio analogue, or a derivative thereof, and a nitrogen atom attached to the same carbon skeleton by a single or double bond, this nitrogen atom not being a member of a derivative or of a thio analogue of a carboxylic group, e.g. amino-carboxylic acids
    • A01N37/46—N-acyl derivatives
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
    • A01N43/48—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with two nitrogen atoms as the only ring hetero atoms
    • A01N43/56—1,2-Diazoles; Hydrogenated 1,2-diazoles
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
    • A01N43/90—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having two or more relevant hetero rings, condensed among themselves or with a common carbocyclic ring system
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D209/00—Heterocyclic compounds containing five-membered rings, condensed with other rings, with one nitrogen atom as the only ring hetero atom
    • C07D209/02—Heterocyclic compounds containing five-membered rings, condensed with other rings, with one nitrogen atom as the only ring hetero atom condensed with one carbocyclic ring
    • C07D209/44—Iso-indoles; Hydrogenated iso-indoles
    • C07D209/48—Iso-indoles; Hydrogenated iso-indoles with oxygen atoms in positions 1 and 3, e.g. phthalimide
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D231/00—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings
    • C07D231/54—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings condensed with carbocyclic rings or ring systems
    • C07D231/56—Benzopyrazoles; Hydrogenated benzopyrazoles
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D513/00—Heterocyclic compounds containing in the condensed system at least one hetero ring having nitrogen and sulfur atoms as the only ring hetero atoms, not provided for in groups C07D463/00, C07D477/00 or C07D499/00 - C07D507/00
    • C07D513/02—Heterocyclic compounds containing in the condensed system at least one hetero ring having nitrogen and sulfur atoms as the only ring hetero atoms, not provided for in groups C07D463/00, C07D477/00 or C07D499/00 - C07D507/00 in which the condensed system contains two hetero rings
    • C07D513/04—Ortho-condensed systems

Definitions

  • the invention further relates to processes for the preparation of these compounds and herbicidal compositions and processes for defoliation (desiccation) of cotton.
  • the object of the invention was to provide compounds which are particularly effective as herbicides. Furthermore, the compounds should be usable as bioregulators, in particular for the defoliation of cotton.
  • the compounds of the formula I are obtained by reacting a suitably substituted benzaldehyde of the formula II with a phosphorane of the formula III in a manner known per se, for example analogously to the conditions described in Synthesis 10 (1984) 862, in a solvent at temperatures between 0 ° C and the boiling point of the solvent:
  • Ar in formula III means an unsubstituted or substituted aryl radical, with the phenyl radical generally being preferred.
  • phosphoranes III required for the preparation of the styrene derivatives I which are also referred to as phosphorus ylides, are based on methods known from the literature (for example Houben-Weyl, Methods of Organic Chemistry, Vol. E1, pp. 636-639, Georg-Thieme Verlag, Stuttgart 1982 or Chem. Ber. 95 , 1962, page 3993).
  • the Ar groups of these phosphoranes can be unsubstituted or substituted phenyl radicals.
  • the number of substituents per phenyl radical and the substitution pattern of the phenyl radicals are generally not critical for the success of the process, but in general a phenyl radical carries no more than 3 substituents.
  • Preferred substituents for the phenyl radicals are those which are inert under the conditions of the process, for example the halides fluorine, chlorine and bromine, alkyl groups, preferably C 1 to C 4 alkyl groups, in particular the methyl group, or C 1 to C 4 -Alkoxy groups, especially the methoxy group.
  • triarylphosphoranes III with an unsubstituted phenyl radical are generally preferred.
  • the reaction of the starting compounds II and III is generally carried out advantageously in the presence of a solvent.
  • solvents all can usually be carried out solvents used by Wittig reactions are used, for example halogenated solvents such as chloroform, or ethers such as tetrahydrofuran, dioxane and ethylene glycol dimethyl ether.
  • Preferred solvents are alcohols, especially C 1 to C 4 alcohols such as methanol, ethanol, propanol, isopropanol, butanol, isobutanol and tert-butanol.
  • the solvents can also be used in the form of solvent mixtures, but the pure solvents are generally preferred.
  • reaction is carried out at temperatures between 0 ° C and 100 ° C.
  • the optimum reaction temperature depends on the starting compounds II and III to be reacted in each case and on the solvent used.
  • the starting compounds II and III can be reacted with one another in stoichiometric amounts. However, it may prove advantageous if one of the two reactants, II or III, is used in a 0.05-5-fold molar excess in the reaction.
  • the course of the Wittig reaction can be followed using conventional analytical methods such as thin layer chromatography and high pressure liquid chromatography.
  • the product I can be isolated by conventional methods such as filtration, centrifugation or by adding water with subsequent extraction. If desired, the styrene derivatives I thus obtained can be purified further, for example by recrystallization or by means of chromatographic methods.
  • the styrene derivatives I are generally obtained as cis-trans isomer mixtures with respect to the alkenyl side chain, the trans isomer generally predominating.
  • the process for the preparation of the styrene derivatives of the formula I also includes the possibility of interchanging the sequence in the synthesis of the benzaldehydes of the general formula II and the Wittig olefination.
  • benzaldehydes of the general formula II used as starting material are easily accessible by the methods of DE-A 38 15 042 ( ⁇ EP-A 340 708) or can be prepared, for example, as described below.
  • the benzaldehydes of the formula IIc are obtained, if an aniline derivative of the formula IV is first converted into the corresponding isothiocyanate V using thiophosgene in accordance with the conditions described for IX, V is added to a piperazine VI, and the thiourea derivative VII thus obtained is added with acidic cleavage of the acetal group Aldehyde function with a phosgenating agent or cyclized to aldehyde IIc, d:
  • V, VII, VIII, B denotes an ethylene or propylene unit which can carry one to three alkyl groups such as methyl, ethyl, propyl and 1-methylethyl, preferably methyl.
  • the dotted line in the formulas VI, VII, VIII and IIc, d stands for a ⁇ bond that may be present.
  • the acetal group in compound VIII is converted into the aldehyde function under acidic conditions, for example in the presence of mineral acids such as hydrochloric acid and sulfuric acid or organic acids such as p-toluenesulfonic acid.
  • the compounds I with the radicals A 1 and A 2 are also obtained, for example, by condensing an aniline of the general formula IX with anhydrides of the general formula Xa or Xb:
  • Inert organic solvents such as lower alkanoic acids such as acetic acid, propionic acid and isobutyric acid and the esters of these acids such as ethyl acetate, higher-boiling hydrocarbons such as toluene and xylene and / or dimethylformamide are used for the condensation.
  • the reaction is usually carried out at temperatures between 25 ° C. and the boiling point of the respective reaction mixture, preferably between 50 and 140 ° C. When using an aprotic solvent, it is advisable to remove the water continuously.
  • Anilines IX are obtained, for example, by reduction from the corresponding nitroderivatives in analogy to known methods (DE-A 37 24 399, DE-A 36 03 789):
  • a nitrostyrene XII is converted to aniline derivative IX in a manner known per se using inorganic compounds such as tin-II salts or iron or tin or by catalytic hydrogenation on metal contacts such as Raney nickel, palladium and platinum in an inert organic solvent reduced.
  • Suitable solvents for the reaction with inorganic compounds are, for example, alcohols such as methanol, ethanol and isopropanol and lower alkanoic acids such as formic acid, acetic acid and propionic acid and corresponding mixtures.
  • the reaction temperatures are 25 ° C to 150 ° C, preferably 25 ° C to 100 ° C.
  • solvents such as methanol or other alcohols, dimethylformamide, propionic acid, tetrahydrofuran and glacial acetic acid and corresponding mixtures at a hydrogen pressure of 1 to 150 bar, preferably 1 to 50 bar and temperatures of 25 ° C. to 100 ° C, preferably 25 to 70 ° C.
  • the compounds Ic, d are also obtained, for example, by reacting a derivative of the general formula IX in a manner known per se (Houben-Weyl, Vol. IX, pp. 867 f. (1955)) in an inert organic solvent with thiophosgene converted into the corresponding isothiocyanate XIII, XIII then added in an aprotic polar solvent to a tetrahydro or perhydrodiazine derivative VI and the thiourea thus obtained XIV cyclized with a phosgenating agent or thiophosgenating agent (Phos.)
  • a phosgenating agent or thiophosgenating agent Phos.
  • reaction of derivative IX with thiophosgene generally takes place at temperatures from (-50) ° C. to 100 ° C., preferably 0 ° C. to 50 ° C.
  • This reaction can be carried out both in a two-phase solvent system such as methylene chloride / water and in the presence of a base in an aprotic polar organic solvent.
  • toluene in the presence of an organic base, preferably a tertiary amine such as triethylamine.
  • the reaction of the isothiocyanates XIII with the piperazines VI is preferably carried out in aprotic polar solvents such as preferably ethers, in particular tetrahydrofuran at temperatures from (-50) ° C. to 100 ° C., preferably 0 ° C. to 50 ° C.
  • aprotic polar solvents such as preferably ethers, in particular tetrahydrofuran at temperatures from (-50) ° C. to 100 ° C., preferably 0 ° C. to 50 ° C.
  • the subsequent cyclization of thiourea XIV with a phosgenating agent or thiophosgenating agent is usually carried out at temperatures from 0 ° C. to 100 ° C., preferably 20 ° C. to 70 ° C. in an aprotic polar solvent in the presence of a base.
  • Particularly suitable phosgenating agents and thiophosgenating agents are phosgene, thiophosgene and trichloromethyl chloroformate.
  • halogenated hydrocarbons and hydrocarbons are preferably used as solvents.
  • Suitable bases are tertiary amines such as pyridine in particular.
  • the styrene derivatives I can be obtained in the preparation as isomer mixtures, enantiomer or diastereomer mixtures and in particular E / Z isomer mixtures being possible. If desired, the isomer mixtures can be prepared by the usual methods, e.g. be separated by chromatography or by crystallization.
  • the styrene derivatives I can be in the form of their agriculturally useful salts.
  • the salts of acids which do not impair the herbicidal activity of I are generally suitable, for example alkali metal salts, in particular the sodium or potassium salt, alkaline earth metal salts, in particular the calcium, magnesium or barium salt, manganese, copper, zinc or iron salt and also ammonium, phosphonium, sulfonium or sulfoxonium salts, for example ammonium salts, tetraalkylammonium salts, benzyltrialkylammonium salts, trialkylsulfonium salts or trialkylsulfoxonium salts.
  • the styrene derivatives I are suitable, both as isomer mixtures and in the form of the pure isomers, as herbicides.
  • the compounds I or the herbicidal and defolianting compositions comprising them can be sprayed, for example in the form of directly sprayable solutions, powders, suspensions, including high-strength aqueous, oily or other suspensions or dispersions, emulsions, oil dispersions, pastes, dusts, sprays or granules. Nebulization, dusting, scattering or pouring can be used.
  • the application forms depend on the purposes; in any case, they should ensure the finest possible distribution of the active compounds according to the invention.
  • the styrene derivatives I are generally suitable for the preparation of directly sprayable solutions, emulsions, pastes or oil dispersions.
  • Mineral oil fractions of medium to high boiling point such as kerosene or diesel oil, furthermore coal tar oils as well as oils of vegetable or animal origin, aliphatic, cyclic and aromatic hydrocarbons, e.g.
  • strongly polar solvents such as N, N-dimethylformamide, dimethyl sulfoxide, N-methylpyrrolidone or water .
  • Aqueous use forms can be prepared from emulsion concentrates, dispersions, pastes, wettable powders or water-dispersible granules by adding water.
  • emulsions, pastes or oil dispersions the substrates as such or dissolved in an oil or solvent can be homogenized in water by means of wetting agents, adhesives, dispersants or emulsifiers.
  • concentrates consisting of an active substance, wetting agent, tackifier, dispersant or emulsifier and possibly solvent or oil, which are suitable for dilution with water.
  • alkali, alkaline earth, ammonium salts of aromatic sulfonic acids e.g. Lignin, phenol, naphthalene and dibutylnaphthalenesulfonic acid, as well as of fatty acids, alkyl and alkylarylsulfonates, alkyl, lauryl ether and fatty alcohol sulfates, and salts of sulfated hexa-, hepta- and octadecanols, as well as fatty alcohol glycol ethers, condensation products of sulfonated naphthalene and its derivatives with formaldehyde, condensation products of naphthalene or naphthalenesulfonic acids with phenol and formaldehyde, polyoxyethylene octylphenol ether, ethoxylated isooctyl, octyl or nonylphenol, alkylphenyl, tributylphenyl poly
  • Powders, materials for broadcasting and dusts can be prepared by mixing or grinding the active substances together with a solid carrier.
  • Granules e.g. Coated, impregnated and homogeneous granules can be produced by binding the active ingredients to solid carriers.
  • Solid carriers are mineral earths like. Silicas, silica gels, silicates, talc, kaolin, limestone, lime, chalk, bolus, loess, clay, dolomite, diatomaceous earth, calcium and magnesium sulfate, magnesium oxide, ground plastics, fertilizers such as ammonium sulfate, ammonium phosphate, ammonium nitrate, ureas and vegetable products such as cereal flour , Tree bark, wood and nutshell flour, cellulose powder or other solid carriers.
  • the formulations contain between 0.01 and 95% by weight, preferably between 0.5 and 90% by weight, of active ingredient.
  • the active ingredients are used in a purity of 90% to 100%, preferably 95% to 100% (according to the NMR spectrum).
  • the herbicidal compositions or the active compounds can be applied pre- or post-emergence. If the active ingredients are less compatible with certain crop plants, application techniques can be used in which the herbicidal compositions are sprayed with the aid of sprayers in such a way that the leaves of the sensitive crop plants are not hit as far as possible, while the active ingredients are applied to the leaves of undesirable plants growing below them or the uncovered floor area (post-directed, lay-by).
  • the application rates of active ingredient are 0.001 to 3, preferably 0.01 to 1 kg / ha of active substance (a.S.).
  • the compounds I can also be used for the desiccation of cotton, since they promote the formation of separating tissue between the leaf and shoot part of the plant.
  • the compounds according to the invention or compositions containing them can also be used in a further number of crop plants for eliminating unwanted plants.
  • the following crops are considered, for example:
  • the styrene derivatives I can be mixed with numerous representatives of other herbicidal or growth-regulating active compound groups and applied together.
  • Plastic flower pots with loamy sand with about 3.0% humus as substrate served as culture vessels.
  • the seeds of the test plants were sown separately according to species.
  • the active ingredients suspended or emulsified in water were applied directly after sowing using finely distributing nozzles.
  • the tubes were lightly sprinkled to promote germination and growth and then covered with clear plastic hoods until the plants had grown. This cover causes the test plants to germinate evenly, unless this was affected by the active ingredients.
  • test plants were treated with the active ingredients suspended or emulsified in water only at a growth height of 3 to 15 cm, depending on the growth habit.
  • the application rate for post-emergence treatment was 0.03 kg / ha as
  • the plants were kept at 10-25 ° C and 20-35 ° C depending on the species.
  • the trial period lasted 2 to 4 weeks. During this time, the plants were cared for and their response to the individual treatments was evaluated.
  • Evaluation was carried out on a scale from 0 to 100. 100 means no emergence of the plants or complete destruction of at least the aerial parts and 0 means no damage or normal growth.
  • the plants used in the greenhouse experiments are composed of the following types: Latin name German name Abutilon theophrasti Chinese hemp Amaranthus retroflexus Curved foxtail Oryza sativa rice Solanum nigrum Black nightshade Ipomoea subspecies Magnificent wind species Triticum aestivum Summer wheat

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Agronomy & Crop Science (AREA)
  • Pest Control & Pesticides (AREA)
  • Plant Pathology (AREA)
  • Health & Medical Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Dentistry (AREA)
  • General Health & Medical Sciences (AREA)
  • Wood Science & Technology (AREA)
  • Zoology (AREA)
  • Environmental Sciences (AREA)
  • Agricultural Chemicals And Associated Chemicals (AREA)
  • Pyrrole Compounds (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
  • Nitrogen And Oxygen Or Sulfur-Condensed Heterocyclic Ring Systems (AREA)
  • Indole Compounds (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Preparation Of Compounds By Using Micro-Organisms (AREA)
  • Saccharide Compounds (AREA)

Abstract

Styrene derivatives I <IMAGE> (R<1> = H; R<2> = halogen; R<3> = H, halogen, C1-C4-alkyl; R<4> = CN, C1-C6-alkylcarbonyl; A = a heterocyclic radical A1 to A5 <IMAGE> where R<5> and R<6> are H, CH3 or C2H5, n is 0 or 1 and X is oxygen or sulphur), with the proviso that R<4> is an alkylcarboxyl group if R<1> represents H and simultaneously A represents A2 where n = 0; and their agriculturally useful salts, the preparation of the styrene derivatives I and herbicidal agents containing them.

Description

Die vorliegende Erfindung betrifft neue Styrolderivate der allgemeinen Formel I

Figure imgb0001
in der die Substituenten folgende Bedeutung haben:

R1
Wasserstoff oder Halogen;
R2
Halogen;
R3
Wasserstoff, Halogen oder C1-C4-Alkyl;
R4
Cyano oder C1-C6-Alkylcarbonyl;
A
einen heterocyclischen Rest, ausgewählt aus der Gruppe A1 bis A4
Figure imgb0002
 wobei R5 und R6 Wasserstoff, Methyl oder Ethyl bedeuten, n für 0 oder 1 und X für Sauerstoff oder Schwefel stehen;
mit der Maßgabe, daß R2 Chlor und R4 C1-C6-Alkylcarbonyl bedeuten, wenn A für den Rest A2 steht;
sowie deren landwirtschaftlich brauchbaren Salze, wobei die Formel I sämtliche isomere Formen dieser Verbindungen umfaßt.The present invention relates to new styrene derivatives of the general formula I.
Figure imgb0001
 in which the substituents have the following meaning:
R 1
Hydrogen or halogen;
R 2
Halogen;
R 3
Hydrogen, halogen or C 1 -C 4 alkyl;
R 4
Cyano or C 1 -C 6 alkylcarbonyl;
A
a heterocyclic radical selected from the group A 1 to A 4
Figure imgb0002
 where R 5 and R 6 are hydrogen, methyl or ethyl, n is 0 or 1 and X is oxygen or sulfur;
with the proviso that R 2 is chlorine and R 4 is C 1 -C 6 alkylcarbonyl when A is the radical A 2 ;
and their agriculturally useful salts, the formula I encompassing all isomeric forms of these compounds.

Des weiteren betrifft die Erfindung Verfahren zur Herstellung dieser Verbindungen sowie herbizide Mittel und Verfahren zur Entblätterung (Desikkation) von Baumwolle.The invention further relates to processes for the preparation of these compounds and herbicidal compositions and processes for defoliation (desiccation) of cotton.

Aus der japanischen Offenlegungsschrift JP-A Kokai 27962/1986 und der DE-A 37 24 399 sind Zimtsäureester der Struktur I' bekannt

Figure imgb0003
Des weiteren werden in der DE-A 37 14 373 N-Phenyl-3,4,5,6-tetrahydrophthalimide als Herbizide beschrieben, die sich von den vorliegenden Verbindungen I mit A = A2 dadurch unterscheiden, daß der Phenylring anstelle des Rests -CH=C(R3,R4) eine mono- oder disubstituierte Methylgruppe trägt.Cinnamic acid esters of structure I 'are known from Japanese published patent application JP-A Kokai 27962/1986 and DE-A 37 24 399
Figure imgb0003
 Furthermore, DE-A 37 14 373 describes N-phenyl-3,4,5,6-tetrahydrophthalimides as herbicides which differ from the present compounds I with A = A 2 in that the phenyl ring instead of the residue - CH = C (R 3 , R 4 ) carries a mono- or disubstituted methyl group.

Außerdem fallen diejenigen Verbindungen I mit A = A2, n = 0, R1 = Wasserstoff und R3 = Wasserstoff, Chlor, Brom oder C1-C4-Alkyl unter die allgemeine Lehre der DE-A 36 03 789, diejenigen mit A = A2, n = 1 und R1 = H oder Fluor unter die allgemeine Lehre der DE-A 39 17 676.In addition, those compounds I with A = A 2 , n = 0, R 1 = hydrogen and R 3 = hydrogen, chlorine, bromine or C 1 -C 4 alkyl fall under the general teaching of DE-A 36 03 789, those with A = A 2 , n = 1 and R 1 = H or fluorine under the general teaching of DE-A 39 17 676.

Da die Verbindungen des o.g. Standes der Technik entweder nicht ausreichende Selektivität aufweisen oder hinsichtlich der benötigten Aufwandmengen zu wünschen übrig lassen, lag der Erfindung die Aufgabe zugrunde, Verbindungen zur Verfügung zu stellen, die herbizid besonders gut wirksam sind. Weiterhin sollten die Verbindungen als Bioregulatoren, insbesondere zur Entblätterung von Baumwolle, verwendbar sein.Since the compounds of the abovementioned prior art either do not have sufficient selectivity or leave anything to be desired in terms of the application rates required, the object of the invention was to provide compounds which are particularly effective as herbicides. Furthermore, the compounds should be usable as bioregulators, in particular for the defoliation of cotton.

Es wurde nun gefunden, daß die eingangs definierten Styrolderivate I auch bei geringen Aufwandmengen eine gute herbizide Wirksamkeit besitzen und sehr gut zur Entblätterung von Baumwolle geeignet sind.It has now been found that the styrene derivatives I defined at the outset have good herbicidal activity even at low application rates and are very suitable for defoliation of cotton.

Man erhält die Verbindungen der Formel I, indem man einen geeignet substituierten Benzaldehyd der Formel II mit einem Phosphoran der Formel III in an sich bekannter Weise, z.B. analog den in Synthesis 10 (1984) 862 beschriebenen Bedingungen, in einem Lösungsmittel bei Temperaturen zwischen 0°C und dem Siedepunkt des Lösungsmittels umsetzt:

Figure imgb0004
The compounds of the formula I are obtained by reacting a suitably substituted benzaldehyde of the formula II with a phosphorane of the formula III in a manner known per se, for example analogously to the conditions described in Synthesis 10 (1984) 862, in a solvent at temperatures between 0 ° C and the boiling point of the solvent:
Figure imgb0004

Ar in Formel III bedeutet einen unsubstituierten oder substituierten Arylrest, wobei im allgemeinen der Phenylrest bevorzugt wird.Ar in formula III means an unsubstituted or substituted aryl radical, with the phenyl radical generally being preferred.

Die zur Herstellung der Styrolderivate I benötigten Phosphorane III, welche auch als Phosphor-Ylide bezeichnet werden, sind nach literaturbekannten Methoden (z.B. Houben-Weyl, Methoden der Organischen Chemie, Bd. E1, S. 636-639, Georg-Thieme Verlag, Stuttgart 1982 oder Chem. Ber. 95, 1962, Seite 3993) erhältlich.The phosphoranes III required for the preparation of the styrene derivatives I, which are also referred to as phosphorus ylides, are based on methods known from the literature (for example Houben-Weyl, Methods of Organic Chemistry, Vol. E1, pp. 636-639, Georg-Thieme Verlag, Stuttgart 1982 or Chem. Ber. 95 , 1962, page 3993).

Die Gruppen Ar dieser Phosphorane können unsubstituierte oder substituierte Phenylreste sein. Die Zahl der Substituenten pro Phenylrest sowie das Substitutionsmuster der Phenylreste sind in der Regel für das Gelingen des Verfahrens nicht kritisch, im allgemeinen trägt ein Phenylrest aber nicht mehr als 3 Substituenten. Als Substituenten der Phenylreste sind solche bevorzugt, welche sich unter den Bedingungen des Verfahrens inert verhalten, z.B. die Halogenide Fluor, Chlor und Brom, Alkylgruppen, bevorzugt C1- bis C4-Alkylgruppen, insbesondere die Methylgruppe, oder C1- bis C4-Alkoxygruppen, insbesondere die Methoxygruppe. Allerdings werden in der Regel Triarylphosphorane III mit unsubstituiertem Phenylrest bevorzugt.The Ar groups of these phosphoranes can be unsubstituted or substituted phenyl radicals. The number of substituents per phenyl radical and the substitution pattern of the phenyl radicals are generally not critical for the success of the process, but in general a phenyl radical carries no more than 3 substituents. Preferred substituents for the phenyl radicals are those which are inert under the conditions of the process, for example the halides fluorine, chlorine and bromine, alkyl groups, preferably C 1 to C 4 alkyl groups, in particular the methyl group, or C 1 to C 4 -Alkoxy groups, especially the methoxy group. However, triarylphosphoranes III with an unsubstituted phenyl radical are generally preferred.

Die Umsetzung der Ausgangsverbindungen II und III wird im allgemeinen vorteilhaft in Gegenwart eines Lösungsmittels durchgeführt. Als Lösungsmittel können alle üblicherweise bei der Durchführung von Wittig-Reaktionen verwendeten Lösungsmittel Anwendung finden, beispielsweise halogenierte Lösungsmittel wie Chloroform, oder Ether wie Tetrahydrofuran, Dioxan und Ethylenglykoldimethylether. Bevorzugte Lösungsmittel sind Alkohole, insbesondere C1- bis C4-Alkohole wie Methanol, Ethanol, Propanol, Isopropanol, Butanol, Isobutanol und tert.-Butanol. Die Lösungsmittel können auch in Form von Lösungsmittelgemischen eingesetzt werden, in der Regel werden jedoch bevorzugt die reinen Lösungsmittel verwendet.The reaction of the starting compounds II and III is generally carried out advantageously in the presence of a solvent. As solvents, all can usually be carried out solvents used by Wittig reactions are used, for example halogenated solvents such as chloroform, or ethers such as tetrahydrofuran, dioxane and ethylene glycol dimethyl ether. Preferred solvents are alcohols, especially C 1 to C 4 alcohols such as methanol, ethanol, propanol, isopropanol, butanol, isobutanol and tert-butanol. The solvents can also be used in the form of solvent mixtures, but the pure solvents are generally preferred.

Im allgemeinen wird die Reaktion bei Temperaturen zwischen 0°C und 100°C ausgeführt. Es versteht sich jedoch von selbst, daß die optimale Reaktionstemperatur von den jeweils umzusetzenden Ausgangsverbindungen II und III sowie dem verwendeten Lösungsmittel abhängig ist.In general, the reaction is carried out at temperatures between 0 ° C and 100 ° C. However, it goes without saying that the optimum reaction temperature depends on the starting compounds II and III to be reacted in each case and on the solvent used.

Die Ausgangsverbindungen II und III können in stöchiometrischen Mengen miteinander umgesetzt werden. Es kann sich jedoch als vorteilhaft erweisen, wenn einer der beiden Reaktanden, II oder III, in einem 0,05-5fachen molaren Überschuß in die Reaktion eingesetzt wird.The starting compounds II and III can be reacted with one another in stoichiometric amounts. However, it may prove advantageous if one of the two reactants, II or III, is used in a 0.05-5-fold molar excess in the reaction.

Der Verlauf der Wittig-Reaktion kann mittels üblicher analytischer Methoden, wie Dünnschichtchromatographie und Hochdruckflüssigkeitschromatographie, verfolgt werden. Nach beendeter Reaktion kann das Produkt I nach herkömmlichen Verfahren wie Filtration, Zentrifugation oder durch Zugabe von Wasser mit anschließender Extraktion isoliert werden. Gewünschtenfalls können die so erhaltenen Styrolderivate I beispielsweise durch Umkristallisation oder mittels chromatographischer Methoden weiter gereinigt werden.The course of the Wittig reaction can be followed using conventional analytical methods such as thin layer chromatography and high pressure liquid chromatography. After the reaction has ended, the product I can be isolated by conventional methods such as filtration, centrifugation or by adding water with subsequent extraction. If desired, the styrene derivatives I thus obtained can be purified further, for example by recrystallization or by means of chromatographic methods.

Nach vorstehendem Verfahren werden die Styrolderivate I hinsichtlich der Alkenylseitenkette im allgemeinen als cis-trans-Isomerengemische erhalten, wobei in der Regel das trans-Isomere überwiegt.According to the above process, the styrene derivatives I are generally obtained as cis-trans isomer mixtures with respect to the alkenyl side chain, the trans isomer generally predominating.

Das Verfahren zur Herstellung der Styrolderivate der Formel I beinhaltet weiterhin die Möglichkeit, die Reihenfolge in der Synthese der Benzaldehyde der allgemeinen Formel II und die Wittig-Olefinierung zu vertauschen.The process for the preparation of the styrene derivatives of the formula I also includes the possibility of interchanging the sequence in the synthesis of the benzaldehydes of the general formula II and the Wittig olefination.

Es besteht insbesondere die Möglichkeit geeignete Vorstufen der Benzaldehyde II mit den Phosphoranen III umzusetzen, und erst dann die entsprechenden Substituenten im Benzaldehydteil zu der Struktur der allgemeinen Formel I zu ergänzen (wie weiter unten beschrieben).In particular, it is possible to implement suitable precursors of the benzaldehydes II with the phosphoranes III and only then to add the corresponding substituents in the benzaldehyde part to the structure of the general formula I (as described below).

Die als Ausgangsmaterial verwendeten Benzaldehyde der allgemeinen Formel II sind nach den Methoden der DE-A 38 15 042 (≙ EP-A 340 708) auf einfache Weise zugänglich oder können beispielsweise wie nachfolgend beschrieben hergestellt werden.The benzaldehydes of the general formula II used as starting material are easily accessible by the methods of DE-A 38 15 042 (≙ EP-A 340 708) or can be prepared, for example, as described below.

Man erhält die Benzaldehyde der Formel IIc, d wenn man ein Anilinderivat der Formel IV entsprechend den für IX geschilderten Bedingungen zuerst mit Thiophosgen in das entsprechende Isothiocyanat V überführt, V an ein Piperazin VI addiert, das so erhaltene Thioharnstoffderivat VII unter saurer Spaltung der Acetalgruppe zur Aldehydfunktion mit einem Phosgenierungsmittel oder zum Aldehyd IIc, d cyclisiert:

Figure imgb0005
The benzaldehydes of the formula IIc are obtained, if an aniline derivative of the formula IV is first converted into the corresponding isothiocyanate V using thiophosgene in accordance with the conditions described for IX, V is added to a piperazine VI, and the thiourea derivative VII thus obtained is added with acidic cleavage of the acetal group Aldehyde function with a phosgenating agent or cyclized to aldehyde IIc, d:
Figure imgb0005

In den Formeln IV, V, VII, VIII bedeutet B eine Ethylen- oder Propyleneinheit, welche ein bis drei Alkylgruppen wie Methyl, Ethyl, Propyl und 1-Methylethyl, vorzugsweise Methyl, tragen kann. Die gepunktete Linie in den Formeln VI, VII, VIII und IIc, d steht für eine ggf. vorhandene π-Bindung.In the formulas IV, V, VII, VIII, B denotes an ethylene or propylene unit which can carry one to three alkyl groups such as methyl, ethyl, propyl and 1-methylethyl, preferably methyl. The dotted line in the formulas VI, VII, VIII and IIc, d stands for a π bond that may be present.

Die Umsetzungen von IV zu V, von V zu VII und von VII zu VIII verlaufen unter den nachstehend geschilderten Bedingungen analog zur zweiten Synthesevariante von Ic, d.The reactions from IV to V, from V to VII and from VII to VIII proceed under the conditions described below analogously to the second synthesis variant of Ic, i.

Die Acetalgruppe in Verbindung VIII wird unter sauren Bedingungen beispielsweise in Gegenwart von Mineralsäuren wie Salzsäure und Schwefelsäure oder organischen Säuren wie p-Toluolsulfonsäure in die Aldehydfunktion übergeführt.The acetal group in compound VIII is converted into the aldehyde function under acidic conditions, for example in the presence of mineral acids such as hydrochloric acid and sulfuric acid or organic acids such as p-toluenesulfonic acid.

Man erhält die Verbindungen I mit den Resten A1 und A2 aber beispielsweise auch dadurch, daß man ein Anilin der allgemeinen Formel IX mit Anhydriden der allgemeinen Formel Xa oder Xb kondensiert:

Figure imgb0006
The compounds I with the radicals A 1 and A 2 are also obtained, for example, by condensing an aniline of the general formula IX with anhydrides of the general formula Xa or Xb:
Figure imgb0006

Für die Kondensation dienen inerte organische Lösungsmittel wie niedere Alkansäuren wie Essigsäure, Propionsäure und Isobuttersäure, sowie die Ester dieser Säuren wie Essigsäureethylester, höhersiedende Kohlenwasserstoffe wie Toluol und Xylol und/oder Dimethylformamid. Die Umsetzung erfolgt in der Regel bei Temperaturen zwischen 25°C und dem Siedepunkt der jeweiligen Reaktionsmischung, vorzugsweise zwischen 50 und 140°C. Bei Verwendung eines aprotischen Lösungsmittels empfiehlt es sich, das Wasser fortlaufend zu entfernen.Inert organic solvents such as lower alkanoic acids such as acetic acid, propionic acid and isobutyric acid and the esters of these acids such as ethyl acetate, higher-boiling hydrocarbons such as toluene and xylene and / or dimethylformamide are used for the condensation. The reaction is usually carried out at temperatures between 25 ° C. and the boiling point of the respective reaction mixture, preferably between 50 and 140 ° C. When using an aprotic solvent, it is advisable to remove the water continuously.

Die Aniline IX erhält man beispielsweise durch Reduktion aus den entsprechenden Nitroderivaten analog bekannter Methoden (DE-A 37 24 399, DE-A 36 03 789):

Figure imgb0007
Anilines IX are obtained, for example, by reduction from the corresponding nitroderivatives in analogy to known methods (DE-A 37 24 399, DE-A 36 03 789):
Figure imgb0007

Die Umsetzung der Nitrobenzaldehyde XI mit den Phosphoranen III erfolgt analog zu den oben beschriebenen Methoden.The reaction of the nitrobenzaldehydes XI with the phosphoranes III is carried out analogously to the methods described above.

In der zweiten Stufe der Reaktionsfolge wird ein Nitrostyrol XII in an sich bekannter Weise mit anorganischen Verbindungen wie Zinn-II-salzen oder Eisen oder Zinn oder durch katalytische Hydrierung an Metallkontakten wie Raney-Nickel, Palladium und Platin in einem inerten organischen Lösungsmittel zum Anilinderivat IX reduziert.In the second stage of the reaction sequence, a nitrostyrene XII is converted to aniline derivative IX in a manner known per se using inorganic compounds such as tin-II salts or iron or tin or by catalytic hydrogenation on metal contacts such as Raney nickel, palladium and platinum in an inert organic solvent reduced.

Geeignete Lösungsmittel für die Reaktion mit anorganischen Verbindungen sind beispielsweise Alkohole wie Methanol, Ethanol und Isopropanol und niedere Alkansäuren wie Ameisensäure, Essigsäure und Propionsäure sowie entsprechende Gemische. Die Reaktionstemperaturen liegen bei 25°C bis 150°C, vorzugsweise bei 25°C bis 100°C.Suitable solvents for the reaction with inorganic compounds are, for example, alcohols such as methanol, ethanol and isopropanol and lower alkanoic acids such as formic acid, acetic acid and propionic acid and corresponding mixtures. The reaction temperatures are 25 ° C to 150 ° C, preferably 25 ° C to 100 ° C.

Sofern man die Reduktion an Metallkontakten mit Wasserstoff durchführt, eignen sich Lösungsmittel wie Methanol oder andere Alkohole, Dimethylformamid, Propionsäure, Tetrahydrofuran und Eisessig und entsprechende Gemische bei einem Wasserstoffdruck von 1 bis 150 bar, vorzugsweise 1 bis 50 bar und Temperaturen von 25°C bis 100°C, vorzugsweise 25 bis 70°C.If the reduction is carried out on metal contacts with hydrogen, solvents such as methanol or other alcohols, dimethylformamide, propionic acid, tetrahydrofuran and glacial acetic acid and corresponding mixtures at a hydrogen pressure of 1 to 150 bar, preferably 1 to 50 bar and temperatures of 25 ° C. to 100 ° C, preferably 25 to 70 ° C.

Man erhält die Verbindungen Ic, d beispielsweise aber auch dadurch, daß man ein Derivat der allgemeinen Formel IX in an sich bekannter Weise (Houben-Weyl, Bd. IX, S. 867 f. (1955)) in einem inerten organischen Lösungsmittel mit Thiophosgen in das entsprechende Isothiocyanat XIII überführt, XIII anschließend in einem aprotisch polaren Lösungsmittel an ein Tetrahydro- oder Perhydrodiazinderivat VI addiert und den so erhaltenen Thioharnstoff XIV mit einem Phosgenierungsmittel oder Thiophosgenierungsmittel (Phos.) zu Ic, d cyclisiert:

Figure imgb0008
The compounds Ic, d are also obtained, for example, by reacting a derivative of the general formula IX in a manner known per se (Houben-Weyl, Vol. IX, pp. 867 f. (1955)) in an inert organic solvent with thiophosgene converted into the corresponding isothiocyanate XIII, XIII then added in an aprotic polar solvent to a tetrahydro or perhydrodiazine derivative VI and the thiourea thus obtained XIV cyclized with a phosgenating agent or thiophosgenating agent (Phos.) To Ic, d:
Figure imgb0008

Die Umsetzung des Derivats IX mit Thiophosgen erfolgt in der Regel bei Temperaturen von (-50)°C bis 100°C, vorzugsweise 0°C bis 50°C.The reaction of derivative IX with thiophosgene generally takes place at temperatures from (-50) ° C. to 100 ° C., preferably 0 ° C. to 50 ° C.

Diese Umsetzung kann sowohl in einem Zweiphasen-Lösungsmittelsystem wie Methylenchlorid/Wasser als auch in Gegenwart einer Base in einem aprotisch polaren organischen Lösungsmittel durchgeführt werden.This reaction can be carried out both in a two-phase solvent system such as methylene chloride / water and in the presence of a base in an aprotic polar organic solvent.

Im letztgenannten Fall arbeitet man bevorzugt in Toluol in Gegenwart einer organischen Base, vorzugsweise eines tertiären Amins wie Triethylamin.In the latter case, it is preferred to work in toluene in the presence of an organic base, preferably a tertiary amine such as triethylamine.

Die Umsetzung der Isothiocyanate XIII mit den Piperazinen VI erfolgt bevorzugt in aprotisch polaren Lösungsmitteln wie vorzugsweise Ethern, insbesondere Tetrahydrofuran bei Temperaturen von (-50)°C bis 100°C, vorzugsweise 0°C bis 50°C.The reaction of the isothiocyanates XIII with the piperazines VI is preferably carried out in aprotic polar solvents such as preferably ethers, in particular tetrahydrofuran at temperatures from (-50) ° C. to 100 ° C., preferably 0 ° C. to 50 ° C.

Die anschließende Cyclisierung des Thioharnstoffs XIV mit einem Phosgenierungsmittel oder Thiophosgenierungsmittel geschieht in der Regel bei Temperaturen von 0°C bis 100°C, vorzugsweise 20°C bis 70°C in einem aprotisch polaren Lösungsmittel in Gegenwart einer Base.The subsequent cyclization of thiourea XIV with a phosgenating agent or thiophosgenating agent is usually carried out at temperatures from 0 ° C. to 100 ° C., preferably 20 ° C. to 70 ° C. in an aprotic polar solvent in the presence of a base.

Als Phosgenierungsmittel und Thiophosgenierungsmittel eignen sich insbesondere Phosgen, Thiophosgen und Chlorameisensäuretrichlormethylester.Particularly suitable phosgenating agents and thiophosgenating agents are phosgene, thiophosgene and trichloromethyl chloroformate.

Als Lösungsmittel dienen vorzugsweise Ether, Halogenkohlenwasserstoffe und Kohlenwasserstoffe, insbesondere Halogenkohlenwasserstoffe wie Methylenchlorid.Ether, halogenated hydrocarbons and hydrocarbons, in particular halogenated hydrocarbons such as methylene chloride, are preferably used as solvents.

Geeignete Basen Sind tertiäre Amine wie insbesondere Pyridin.Suitable bases are tertiary amines such as pyridine in particular.

Die Styrolderivate I können bei der Herstellung als Isomerengemische anfallen, wobei Enantiomeren- oder Diastereomerengemische und insbesondere E-/Z-Isomerengemische möglich sind. Die Isomerengemische können gewünschtenfalls nach den hierfür üblichen Methoden, z.B. durch Chromatographie oder durch Kristallisation, getrennt werden.The styrene derivatives I can be obtained in the preparation as isomer mixtures, enantiomer or diastereomer mixtures and in particular E / Z isomer mixtures being possible. If desired, the isomer mixtures can be prepared by the usual methods, e.g. be separated by chromatography or by crystallization.

Im Hinblick auf die bestimmungsgemäße Verwendung der Verbindungen I als Herbizide kommen als Substituenten vorzugsweise folgende Reste in Betracht:

R1
Wasserstoff oder Halogen, wie Fluor, Chlor und Brom, insbesondere Wasserstoff oder Fluor;
R2
Halogen wie Fluor, Chlor und Brom, insbesondere Chlor;
R3
Wasserstoff; ein Halogenatom wie unter R2 genannt, aber auch Jod, insbesondere Chlor und Brom; eine verzweigte oder unverzweigte C1-C4-Alkylgruppe wie Methyl, Ethyl, n-Propyl, Isopropyl, n-Butyl, 1-Methylpropyl, 2-Methylpropyl und 1,1-Dimethylethyl, insbesondere Methyl und Ethyl;
R4
Cyano; C1-C6-Alkylcarbonyl, wobei als Alkylreste Methyl, Ethyl, n-Propyl, Isopropyl, n-Butyl, 1-Methylpropyl, 2-Methylpropyl, 1,1-Dimethylethyl, n-Pentyl, 1-Methylbutyl, 2-Methylbutyl, 3-Methylbutyl, 1,2-Dimethylpropyl, 1,1-Dimethylpropyl, 2,2-Dimethylpropyl, 1-Ethylpropyl, n-Hexyl, 1-Methylpentyl, 2-Methylpentyl, 3-Methylpentyl, 4-Methylpentyl, 1,2-Dimethylbutyl, 1,3-Dimethylbutyl, 2,3-Dimethylbutyl, 1,1-Dimethylbutyl, 2,2-Dimethylbutyl, 3,3-Dimethylbutyl, 1,1,2-Trimethylpropyl, 1,2,2-Trimethylpropyl, 1-Ethylbutyl, 2-Ethylbutyl und 1-Ethyl-2-methylpropyl, insbesondere Methyl, Ethyl, n-Propyl und Isopropyl in Betracht kommen;
R5 und R6
Wasserstoff, Methyl und Ethyl.
With regard to the intended use of the compounds I as herbicides, the following radicals are preferably suitable as substituents:
R 1
Hydrogen or halogen, such as fluorine, chlorine and bromine, in particular hydrogen or fluorine;
R 2
Halogen such as fluorine, chlorine and bromine, especially chlorine;
R 3
Hydrogen; a halogen atom as mentioned under R 2 , but also iodine, especially chlorine and bromine; a branched or unbranched C 1 -C 4 alkyl group such as methyl, ethyl, n-propyl, isopropyl, n-butyl, 1-methylpropyl, 2-methylpropyl and 1,1-dimethylethyl, in particular methyl and ethyl;
R 4
Cyano; C 1 -C 6 -alkylcarbonyl, where as alkyl radicals are methyl, ethyl, n-propyl, isopropyl, n-butyl, 1-methylpropyl, 2-methylpropyl, 1,1-dimethylethyl, n-pentyl, 1-methylbutyl, 2-methylbutyl , 3-methylbutyl, 1,2-dimethylpropyl, 1,1-dimethylpropyl, 2,2-dimethylpropyl, 1-ethylpropyl, n-hexyl, 1-methylpentyl, 2-methylpentyl, 3-methylpentyl, 4-methylpentyl, 1,2 -Dimethylbutyl, 1,3-dimethylbutyl, 2,3-dimethylbutyl, 1,1-dimethylbutyl, 2,2-dimethylbutyl, 3,3-dimethylbutyl, 1,1,2-trimethylpropyl, 1,2,2-trimethylpropyl, 1-ethylbutyl, 2-ethylbutyl and 1-ethyl-2-methylpropyl, in particular methyl, ethyl, n-propyl and isopropyl;
R 5 and R 6
Hydrogen, methyl and ethyl.

Die Styrolderivate I können in Form ihrer landwirtschaftlich brauchbaren Salze vorliegen. Allgemein eignen sich die Salze von solchen Säuren, welche die herbizide Wirkung von I nicht beeinträchtigen, beispielsweise Alkalimetallsalze, insbesondere das Natrium- oder Kaliumsalz, Erdalkalisalze, insbesondere das Calcium-, Magnesium- oder Bariumsalz, Mangan-, Kupfer-, Zink- oder Eisensalz sowie Ammonium-, Phosphonium-, Sulfonium- oder Sulfoxoniumsalze, beispielsweise Ammoniumsalze, Tetraalkylammoniumsalze, Benzyltrialkylammoniumsalze, Trialkylsulfoniumsalze oder Trialkylsulfoxoniumslaze.The styrene derivatives I can be in the form of their agriculturally useful salts. The salts of acids which do not impair the herbicidal activity of I are generally suitable, for example alkali metal salts, in particular the sodium or potassium salt, alkaline earth metal salts, in particular the calcium, magnesium or barium salt, manganese, copper, zinc or iron salt and also ammonium, phosphonium, sulfonium or sulfoxonium salts, for example ammonium salts, tetraalkylammonium salts, benzyltrialkylammonium salts, trialkylsulfonium salts or trialkylsulfoxonium salts.

Beispielsweise seien die in den nachstehenden Tabellen 1 bis 5 aufgeführten Verbindungen I genannt.

Figure imgb0009
Figure imgb0010
Figure imgb0011
Figure imgb0012
Figure imgb0013
Figure imgb0014
Figure imgb0015
Figure imgb0016
Figure imgb0017
Figure imgb0018
Figure imgb0019
Figure imgb0020
Figure imgb0021
Figure imgb0022
Figure imgb0023
Figure imgb0024
Figure imgb0025
Figure imgb0026
 For example, the compounds I listed in Tables 1 to 5 below may be mentioned.
Figure imgb0009
Figure imgb0010
Figure imgb0011
Figure imgb0012
Figure imgb0013
Figure imgb0014
Figure imgb0015
Figure imgb0016
Figure imgb0017
Figure imgb0018
Figure imgb0019
Figure imgb0020
Figure imgb0021
Figure imgb0022
Figure imgb0023
Figure imgb0024
Figure imgb0025
Figure imgb0026

Die Styrolderivate I eignen sich, sowohl als Isomerengemische als auch in Form der reinen Isomeren, als Herbizide. Die Verbindungen I bzw. die sie enthaltenden herbiziden und entblätternden Mittel können beispielsweise in Form von direkt versprühbaren Lösungen, Pulvern, Suspensionen, auch hochprozentigen wäßrigen, öligen oder sonstigen Suspensionen oder Dispersionen, Emulsionen, Öldispersionen, Pasten, Stäubemitteln, Streumitteln oder Granulaten durch Versprühen, Vernebeln, Verstäuben, Verstreuen oder Gießen angewendet werden. Die Anwendungsformen richten sich nach den Verwendungszwecken; sie sollten in jedem Fall möglichst die feinste Verteilung der erfindungsgemäßen Wirkstoffe gewährleisten.The styrene derivatives I are suitable, both as isomer mixtures and in the form of the pure isomers, as herbicides. The compounds I or the herbicidal and defolianting compositions comprising them can be sprayed, for example in the form of directly sprayable solutions, powders, suspensions, including high-strength aqueous, oily or other suspensions or dispersions, emulsions, oil dispersions, pastes, dusts, sprays or granules. Nebulization, dusting, scattering or pouring can be used. The application forms depend on the purposes; in any case, they should ensure the finest possible distribution of the active compounds according to the invention.

Die Styrolderivate I eignen sich allgemein zur Herstellung von direkt versprühbaren Lösungen, Emulsionen, Pasten oder Öldispersionen. Als inerte Zusatzstoffe kommen Mineralölfraktionen von mittlerem bis hohem Siedepunkt, wie Kerosin oder Dieselöl, ferner Kohlenteeröle sowie Öle pflanzlichen oder tierischen Ursprungs, aliphatische, cyclische und aromatische Kohlenwasserstoffe, z.B. Toluol, Xylol, Paraffin, Tetrahydronaphthalin, alkylierte Naphthaline oder deren Derivate, Methanol, Ethanol, Propanol, Butanol, Cyclohexanol, Cyclohexanon, Chlorbenzol, Isophoron oder stark polare Lösungsmittel, wie N,N-Dimethylformamid, Dimethylsulfoxid, N-Methylpyrrolidon oder Wasser in Betracht.The styrene derivatives I are generally suitable for the preparation of directly sprayable solutions, emulsions, pastes or oil dispersions. Mineral oil fractions of medium to high boiling point, such as kerosene or diesel oil, furthermore coal tar oils as well as oils of vegetable or animal origin, aliphatic, cyclic and aromatic hydrocarbons, e.g. Toluene, xylene, paraffin, tetrahydronaphthalene, alkylated naphthalenes or their derivatives, methanol, ethanol, propanol, butanol, cyclohexanol, cyclohexanone, chlorobenzene, isophorone or strongly polar solvents, such as N, N-dimethylformamide, dimethyl sulfoxide, N-methylpyrrolidone or water .

Wäßrige Anwendungsformen können aus Emulsionskonzentraten, Dispersionen, Pasten, netzbaren Pulvern oder wasserdispergierbaren Granulaten durch Zusatz von Wasser bereitet werden. Zur Herstellung von Emulsionen, Pasten oder Öldispersionen können die Substrate als solche oder in einem Öl oder Lösungsmittel gelöst, mittels Netz-, Haft-, Dispergier- oder Emulgiermittel in Wasser homogenisiert werden. Es können aber auch aus wirksamer Substanz, Netz-, Haft-, Dispergier- oder Emulgiermittel und eventuell Lösungsmittel oder Öl bestehende Konzentrate hergestellt werden, die zur Verdünnung mit Wasser geeignet sind.Aqueous use forms can be prepared from emulsion concentrates, dispersions, pastes, wettable powders or water-dispersible granules by adding water. To prepare emulsions, pastes or oil dispersions, the substrates as such or dissolved in an oil or solvent can be homogenized in water by means of wetting agents, adhesives, dispersants or emulsifiers. However, it is also possible to prepare concentrates consisting of an active substance, wetting agent, tackifier, dispersant or emulsifier and possibly solvent or oil, which are suitable for dilution with water.

Als oberflächenaktive Stoffe kommen die Alkali-, Erdalkali-, Ammoniumsalze von aromatischen Sulfonsäuren, z.B. Lignin-, Phenol-, Naphthalin- und Dibutylnaphthalinsulfonsäure, sowie von Fettsäuren, Alkyl- und Alkylarylsulfonaten, Alkyl-, Laurylether- und Fettalkoholsulfaten, sowie Salze sulfatierter Hexa-, Hepta- und Octadecanolen, sowie von Fettalkoholglykolether, Kondensationsprodukte von sulfoniertem Naphthalin und seiner Derivate mit Formaldehyd, Kondensationsprodukte des Naphthalins bzw. der Naphthalinsulfonsäuren mit Phenol und Formaldehyd, Polyoxyethylenoctylphenolether, ethoxyliertes Isooctyl-, Octyl- oder Nonylphenol, Alkylphenyl-, Tributylphenylpolyglykolether, Alkylarylpolyetheralkohole, Isotridecylalkohol, Fettalkoholethylenoxid-Kondensate, ethoxyliertes Rizinusöl, Polyoxyethylenalkylether oder Polyoxypropylenalkylether, Laurylalkoholpolyglykoletheracetat, Sorbitester, Lignin-Sulfitablaugen oder Methylcellulose in Betracht.The alkali, alkaline earth, ammonium salts of aromatic sulfonic acids, e.g. Lignin, phenol, naphthalene and dibutylnaphthalenesulfonic acid, as well as of fatty acids, alkyl and alkylarylsulfonates, alkyl, lauryl ether and fatty alcohol sulfates, and salts of sulfated hexa-, hepta- and octadecanols, as well as fatty alcohol glycol ethers, condensation products of sulfonated naphthalene and its derivatives with formaldehyde, condensation products of naphthalene or naphthalenesulfonic acids with phenol and formaldehyde, polyoxyethylene octylphenol ether, ethoxylated isooctyl, octyl or nonylphenol, alkylphenyl, tributylphenyl polyglycol ether, alkylaryl polyether alcohols, isotridecyl alcohol, polyether ethoxylate, fatty alcohol, ethoxylated ethoxylated ethoxylated alcohol, fatty alcohol ethoxylated ethoxylated ethoxylated alcohol, fatty alcohol ethoxylated ethoxylated polyether Lignin liquor or methyl cellulose into consideration.

Pulver-, Streu- und Stäubemittel können durch Mischen oder gemeinsames Vermahlen der wirksamen Substanzen mit einem festen Trägerstoff hergestellt werden.Powders, materials for broadcasting and dusts can be prepared by mixing or grinding the active substances together with a solid carrier.

Granulate, z.B. Umhüllungs-, Imprägnierungs- und Homogengranulate können durch Bindung der Wirkstoffe an feste Trägerstoffe hergestellt werden. Feste Trägerstoffe sind Mineralerden wie . Kieselsäuren, Kieselgele, Silikate, Talkum, Kaolin, Kalkstein, Kalk, Kreide, Bolus, Löß, Ton, Dolomit, Diatomeenerde, Calcium- und Magnesiumsulfat, Magnesiumoxid, gemahlene Kunststoffe, Düngemittel wie Ammoniumsulfat, Ammoniumphosphat, Ammoniumnitrat, Harnstoffe und pflanzliche Produkte wie Getreidemehl, Baumrinden-, Holz- und Nußschalenmehl, Cellulosepulver oder andere feste Trägerstoffe.Granules, e.g. Coated, impregnated and homogeneous granules can be produced by binding the active ingredients to solid carriers. Solid carriers are mineral earths like. Silicas, silica gels, silicates, talc, kaolin, limestone, lime, chalk, bolus, loess, clay, dolomite, diatomaceous earth, calcium and magnesium sulfate, magnesium oxide, ground plastics, fertilizers such as ammonium sulfate, ammonium phosphate, ammonium nitrate, ureas and vegetable products such as cereal flour , Tree bark, wood and nutshell flour, cellulose powder or other solid carriers.

Die Formulierungen enthalten zwischen 0,01 und 95 Gew.%, vorzugsweise zwischen 0,5 und 90 Gew.%, Wirkstoff. Die Wirkstoffe werden dabei in einer Reinheit von 90 % bis 100 %, vorzugsweise 95 % bis 100 % (nach NMR-Spektrum) eingesetzt.The formulations contain between 0.01 and 95% by weight, preferably between 0.5 and 90% by weight, of active ingredient. The active ingredients are used in a purity of 90% to 100%, preferably 95% to 100% (according to the NMR spectrum).

Die erfindungsgemäßen Verbindungen I können beispielsweise wie folgt formuliert werden:

  • I. Man vermischt 90 Gewichtsteile der Verbindung Nr. 2 mit 10 Gewichtsteilen N-Methyl-α-pyrrolidon und erhält eine Lösung, die zur Anwendung in Form kleinster Tropfen geeignet ist.
  • II. 20 Gewichtsteile der Verbindung Nr. 3 werden in einer Mischung gelöst, die aus 80 Gewichtsteilen Xylol, 10 Gewichtsteilen des Anlagerungsproduktes von 8 bis 10 Mol Ethylenoxid an 1 Mol Ölsäure-N-monoethanolamid, 5 Gewichtsteilen Calciumsalz der Dodecylbenzolsulfonsäure und 5 Gewichtsteilen des Anlagerungsproduktes von 40 Mol Ethylenoxid an 1 Mol Ricinusöl besteht. Durch Ausgießen und feines Verteilen der Lösung in 100 000 Gewichtsteilen Wasser erhält man eine wäßrige Dispersion, die 0,02 Gew.% des Wirkstoffs enthält.
  • III. 20 Gewichtsteile des Wirkstoffs Nr. 4 werden mit 3 Gewichtsteilen des Natriumsalzes der Diisobutylnaphthalin-α-sulfonsäure, 17 Gewichtsteilen des Natriumsalzes einer Ligninsulfonsäure aus einer Sulfit-Ablauge und 60 Gewichtsteilen pulverförmigem Kieselsäuregel gut vermischt und in einer Hammermühle vermahlen. Durch feines Verteilen der Mischung in 20 000 Gewichtsteilen Wasser erhält man eine Spritzbrühe, die 0,1 Gew.% des Wirkstoffs enthält.
  • IV. 3 Gewichtsteile des Wirkstoffs Nr. 6 werden mit 97 Gewichtsteilen feinteiligem Kaolin vermischt. Man erhält auf diese Weise ein Stäubemittel, das 3 Gew.% des Wirkstoffs enthält.
  • V. 30 Gewichtsteile des Wirkstoffs Nr. 7 werden mit einer Mischung aus 92 Gewichtsteilen pulverförmigem Kieselsäuregel und 8 Gewichtsteilen Paraffinöl, das auf die Oberfläche dieses Kieselsäuregels gesprüht wurde, innig vermischt. Man erhält auf diese Weise eine Aufbereitung des Wirkstoffs mit guter Haftfähigkeit.
  • VI. 20 Gewichtsteile des Wirkstoffs Nr. 9 werden mit 2 Gewichtsteilen Calciumsalz der Dodecylbenzolsulfonsäure, 8 Gewichtsteilen Fettalkohol-polyglykolether, 2 Gewichtsteilen Natriumsalz eines Phenol-Harnstoff-Formaldehyd-Kondensates und 68 Gewichtsteilen eines paraffinischen Mineralöls innig vermischt. Man erhält eine stabile ölige Dispersion.
The compounds I according to the invention can be formulated, for example, as follows:
  • I. 90 parts by weight of compound no. 2 are mixed with 10 parts by weight of N-methyl-α-pyrrolidone and a solution is obtained which is suitable for use in the form of tiny drops.
  • II. 20 parts by weight of compound no. 3 are dissolved in a mixture consisting of 80 parts by weight of xylene, 10 parts by weight of the adduct of 8 to 10 moles of ethylene oxide and 1 mole of oleic acid-N-monoethanolamide, 5 parts by weight of calcium salt of dodecylbenzenesulfonic acid and 5 parts by weight of the adduct of 40 moles of ethylene oxide with 1 mole of castor oil. By pouring the solution into 100,000 parts by weight of water and finely distributing it therein, an aqueous dispersion is obtained which contains 0.02% by weight of the active ingredient.
  • III. 20 parts by weight of active ingredient No. 4 are mixed well with 3 parts by weight of the sodium salt of diisobutylnaphthalene-α-sulfonic acid, 17 parts by weight of the sodium salt of lignosulfonic acid from a sulfite waste liquor and 60 parts by weight of powdered silica gel and ground in a hammer mill. By finely distributing the mixture in 20,000 parts by weight of water, a spray liquor is obtained which contains 0.1% by weight of the active ingredient.
  • IV. 3 parts by weight of active ingredient No. 6 are mixed with 97 parts by weight of finely divided kaolin. In this way a dust is obtained which contains 3% by weight of the active ingredient.
  • V. 30 parts by weight of active ingredient No. 7 are intimately mixed with a mixture of 92 parts by weight of powdered silica gel and 8 parts by weight of paraffin oil which has been sprayed onto the surface of this silica gel. In this way, a preparation of the active ingredient with good adhesiveness is obtained.
  • VI. 20 parts by weight of active ingredient No. 9 are intimately mixed with 2 parts by weight of calcium salt of dodecylbenzenesulfonic acid, 8 parts by weight of fatty alcohol polyglycol ether, 2 parts by weight of sodium salt of a phenol-urea-formaldehyde condensate and 68 parts by weight of a paraffinic mineral oil. A stable oily dispersion is obtained.

Die Applikation der herbiziden Mittel bzw. der Wirkstoffe kann im Vorauflauf- oder im Nachauflaufverfahren erfolgen. Sind die Wirkstoffe für gewisse Kulturpflanzen weniger verträglich, so können Ausbringungstechniken angewandt werden, bei welchen die herbiziden Mittel mit Hilfe der Spritzgeräte so gespritzt werden, daß die Blätter der empfindlichen Kulturpflanzen nach Möglichkeit nicht getroffen werden, während die Wirkstoffe auf die Blätter darunter wachsender unerwünschter Pflanzen oder die unbedeckte Bodenfläche gelangen (post-directed, lay-by).The herbicidal compositions or the active compounds can be applied pre- or post-emergence. If the active ingredients are less compatible with certain crop plants, application techniques can be used in which the herbicidal compositions are sprayed with the aid of sprayers in such a way that the leaves of the sensitive crop plants are not hit as far as possible, while the active ingredients are applied to the leaves of undesirable plants growing below them or the uncovered floor area (post-directed, lay-by).

Die Aufwandmengen an Wirkstoff betragen je nach Bekämpfungsziel, Jahreszeit, Zielpflanzen und Wachstumsstadium 0,001 bis 3, vorzugsweise 0,01 bis 1 kg/ha aktive Substanz (a.S.).Depending on the control target, the season, the target plants and the growth stage, the application rates of active ingredient are 0.001 to 3, preferably 0.01 to 1 kg / ha of active substance (a.S.).

Die Verbindungen I können daneben zur Dessikation von Baumwolle eingesetzt werden, da sie die Ausbildung von Trenngewebe zwischen Blatt- und Sproßteil der Pflanze fördern.The compounds I can also be used for the desiccation of cotton, since they promote the formation of separating tissue between the leaf and shoot part of the plant.

Außerdem führt die Verkürzung des Zeitintervalls, in dem die einzelnen Baumwollpflanzen reif werden, zu einer erhöhten Faserqualität nach der Ernte.In addition, the shortening of the time interval in which the individual cotton plants ripen leads to increased fiber quality after the harvest.

In Anbetracht der Vielseitigkeit der Applikationsmethoden können die erfindungsgemäßen Verbindungen bzw. sie enthaltende Mittel noch in einer weiteren Zahl von Kulturplfanzen zur Beseitigung unerwünschter Pflanzen eingesetzt werden. In Betracht kommen beispielsweise folgende Kulturen:

Figure imgb0027
Figure imgb0028
Figure imgb0029
 In view of the versatility of the application methods, the compounds according to the invention or compositions containing them can also be used in a further number of crop plants for eliminating unwanted plants. The following crops are considered, for example:
Figure imgb0027
Figure imgb0028
Figure imgb0029

Zur Verbreiterung des Wirkungsspektrums und zur Erzielung synergistischer Effekte können die Styrolderivate I mit zahlreichen Vertretern anderer herbizider oder wachstumsregulierender Wirkstoffgruppen gemischt und gemeinsam ausgebracht werden. Beispielsweise kommen als Mischungspartner Diazine, 4H-3,1-Benzoxazinderivate, Benzothiadiazinone, 2,6-Dinitroaniline, N-Phenylcarbamate, Thiolcarbamate, Halogencarbonsäuren, Triazine, Amide, Harnstoffe, Diphenylether, Triazinone, Uracile, Benzofuranderivate, Cyclohexan-1,3-dionderivate, Chinolincarbonsäurederivate, Sulfonylharnstoffe, Aryloxy-, Heteroaryloxyphenoxypropionsäuren sowie deren Salze, Ester und Amide und andere in Betracht.To widen the spectrum of activity and to achieve synergistic effects, the styrene derivatives I can be mixed with numerous representatives of other herbicidal or growth-regulating active compound groups and applied together. For example, diazines, 4H-3,1-benzoxazine derivatives, benzothiadiazinones, 2,6-dinitroanilines, N-phenyl carbamates, thiol carbamates, halocarboxylic acids, triazines, amides, ureas, diphenyl ethers, triazinones, uracils, benzofuran derivatives, cyclohexane-1,3- dione derivatives, quinoline carboxylic acid derivatives, sulfonylureas, aryloxy, heteroaryloxyphenoxypropionic acids and their salts, esters and amides and others into consideration.

Außerdem kann es von Nutzen sein, die neuen Verbindungen I allein oder in Kombination mit anderen Herbiziden auch noch mit weiteren Pflanzenschutzmitteln gemischt gemeinsam auszubringen, beispielsweise mit Mitteln zur Bekämpfung von Schädlingen oder phytopathogenen Pilzen bzw. Bakterien. Von Interesse ist ferner die Mischbarkeit mit Mineralsalzlösungen, welche zur Behebung von Ernährungs- und Spurenelementmängeln eingesetzt werden. Es können auch nichtphytotoxische Öle und Ölkonzentrate zugesetzt werden.It may also be useful to apply the new compounds I, alone or in combination with other herbicides, mixed with other crop protection agents, for example with agents for controlling pests or phytopathogenic fungi or bacteria. Also of interest is the miscibility with mineral salt solutions, which are used to remedy nutritional and trace element deficiencies. Non-phytotoxic oils and oil concentrates can also be added.

HerstellungsbeispieleManufacturing examples Beispiel 1example 1 N-(3-(2-Chlorbut-1-en-3-onyl)-4-chlorphenyl)-dimethylmaleinsäureimid (Verbindung Nr. 1)N- (3- (2-chlorobut-1-en-3-onyl) -4-chlorophenyl) dimethyl maleimide (Compound No. 1)

70 ml einer Lösung aus 12,3 g (35 mmol) Acetyl-(chlor)-methylentriphenylphosphoran in Ethanol wurden bei Raumtemperatur vorgelegt und 2,1 g (8 mmol) N-(4-Chlor-3-formylphenyl)-dimethylmaleinsäureimid zugegeben. Nach 4 Stunden Rühren bei ca. 20 bis 25°C kühlte man den Ansatz auf (-10)°C, wonach der Feststoffanteil abgetrennt, mit wenig kaltem Ethanol gewaschen und unter reduziertem Druck bei 40°C getrocknet wurde. Ausbeute: 89 %; Fp.: 173-179°C.70 ml of a solution of 12.3 g (35 mmol) of acetyl- (chloro) methylenetriphenylphosphorane in ethanol were initially introduced at room temperature and 2.1 g (8 mmol) of N- (4-chloro-3-formylphenyl) dimethylmaleimide were added. After 4 hours of stirring at about 20 to 25 ° C, the mixture was cooled to (-10) ° C, after which the solids content was separated off, washed with a little cold ethanol and dried at 40 ° C under reduced pressure. Yield: 89%; Mp: 173-179 ° C.

Beispiel 2Example 2 N-(5-(2-Chlorbut-1-en-3-onyl)-4-chlor-2-fluorphenyl)-4,5,6,7-tetrahydrophthalsäureimid (Verbindung Nr. 2)N- (5- (2-chlorobut-1-en-3-onyl) -4-chloro-2-fluorophenyl) -4,5,6,7-tetrahydrophthalimide (Compound No. 2)

12,3 g (35 mmol) Acetyl-(chlor)-methylentriphenylphosphoran wurden in 70 ml Ethanol vorgelegt und 2,15 g (7 mmol) N-(4-Chlor-2-fluor-5-formylphenyl)-4,5,6,7-tetrahydrophthalsäureimid zugegeben. Man rührte 1 Stunde bei etwa 20°C, kühlte auf (-10)°C ab, saugte ab und wusch mit wenig kaltem Ethanol nach. Durch Einengen der Mutterlauge konnte weiterer Feststoff isoliert werden. Das Rohprodukt wurde unter reduziertem Druck bei 40°C getrocknet. Ausbeute: 67 %; Fp.: 141-142,5°C.12.3 g (35 mmol) of acetyl- (chloro) methylenetriphenylphosphorane were placed in 70 ml of ethanol and 2.15 g (7 mmol) of N- (4-chloro-2-fluoro-5-formylphenyl) -4.5, 6,7-tetrahydrophthalimide added. The mixture was stirred at about 20 ° C for 1 hour, cooled to (-10) ° C, suction filtered and washed with a little cold ethanol. Further solids could be isolated by concentrating the mother liquor. The crude product was dried at 40 ° C under reduced pressure. Yield: 67%; Mp: 141-142.5 ° C.

Beispiel 3Example 3 N-(5-(2-Chlorbut-1-en-3-onyl)-2,4-diffluorphenyl)-4,5,6,7-tetranydrophthalsäureimid (Verbindung Nr. 3)N- (5- (2-chlorobut-1-en-3-onyl) -2,4-diffluorophenyl) -4,5,6,7-tetranydrophthalimide (Compound No. 3)

12,3 g (35 mmol) Acetyl-(chlor)-methylentriphenylphosphoran wurden in 70 ml Ethanol vorgelegt und 2,3 g (8 mmol) N-(2,4-Difluor-5-formylphenyl)-4,5,6,7-tetrahydrophthalsäureimid zugegeben. Man rührte 1 Stunde bei 20 bis 25°C, kühlte auf (-10)°C ab, saugte ab und wusch mit wenig kaltem Ethanol nach. Der Rückstand wurde bei 35°C unter reduziertem Druck getrocknet. Ausbeute: 82 %; Fp.: 170-172°C.12.3 g (35 mmol) of acetyl- (chloro) methylenetriphenylphosphorane were placed in 70 ml of ethanol and 2.3 g (8 mmol) of N- (2,4-difluoro-5-formylphenyl) -4,5,6, 7-tetrahydrophthalimide added. The mixture was stirred at 20 to 25 ° C for 1 hour, cooled to (-10) ° C, suction filtered and washed with a little cold ethanol. The residue was dried at 35 ° C under reduced pressure. Yield: 82%; Mp .: 170-172 ° C.

Analog den Beispielen 2 bis 4 wurden unter entsprechender Abwandlung der Ausgangsverbindungen die in Tabelle 5 aufgelisteten Styrolderivate I hergestellt:

Figure imgb0030
Analogously to Examples 2 to 4, the styrene derivatives I listed in Table 5 were prepared with a corresponding modification of the starting compounds:
Figure imgb0030

Beispiel 4Example 4 N-(3-(2-Chlor-2-cyanoethenyl)-4-chlorphenyl)-dimethylmaleinsäureimid (Verbindung Nr. 7)N- (3- (2-chloro-2-cyanoethenyl) -4-chlorophenyl) dimethyl maleimide (Compound No. 7)

Zu einer Mischung aus 8,4 g (25 mmol) Chlor-(cyano)-methylentriphenylphosphoran in 40 ml Methanol wurden 2,6 g (10 mmol) N-(4-Chlor-3-formylphenyl)-dimethylmaleinsäureimid gegeben. Man rührte 4 Stunden bei etwa 20 bis 25°C und kühlte dann auf (-10)°C ab, wonach der Feststoffanteil abgetrennt und mit wenig kaltem Methanol nachgewaschen wurde. Der Rückstand wurde unter reduziertem Druck bei 30°C getrocknet. Ausbeute: 69 %; Fp.: 139-140,5°C.2.6 g (10 mmol) of N- (4-chloro-3-formylphenyl) dimethylmaleimide were added to a mixture of 8.4 g (25 mmol) of chloro (cyano) methylene triphenylphosphorane in 40 ml of methanol. The mixture was stirred for 4 hours at about 20 to 25 ° C and then cooled to (-10) ° C, after which the solids content was separated and washed with a little cold methanol. The residue was dried at 30 ° C under reduced pressure. Yield: 69%; Mp .: 139-140.5 ° C.

Analog zu Beispiel 4 wurden die Verbindungen der Tabelle 6 hergestellt:

Figure imgb0031
The compounds of Table 6 were prepared analogously to Example 4:
Figure imgb0031

AnwendungsbeispieleExamples of use

Die herbizide Wirkung der Styrolderivate I ließ sich durch Gewächshausversuche zeigen:The herbicidal activity of the styrene derivatives I was demonstrated by greenhouse tests:

Als Kulturgefäße dienten Plastikblumentöpfe mit lehmigem Sand mit etwa 3,0 % Humus als Substrat. Die Samen der Testpflanzen wurden nach Arten getrennt eingesät.Plastic flower pots with loamy sand with about 3.0% humus as substrate served as culture vessels. The seeds of the test plants were sown separately according to species.

Bei Vorauflaufbehandlung wurden die in Wasser suspendierten oder emulgierten Wirkstoffe direkt nach Einsaat mittels fein verteilender Düsen aufgebracht. Die Gefäße wurden leicht beregnet, um Keimung und Wachstum zu fördern und anschließend mit durchsichtigen Plastikhauben abgedeckt, bis die Pflanzen angewachsen waren. Diese Abdeckung bewirkt ein gleichmäßiges Keimen der Testpflanzen, sofern dies nicht durch die Wirkstoffe beeinträchtigt wurde.In pre-emergence treatment, the active ingredients suspended or emulsified in water were applied directly after sowing using finely distributing nozzles. The tubes were lightly sprinkled to promote germination and growth and then covered with clear plastic hoods until the plants had grown. This cover causes the test plants to germinate evenly, unless this was affected by the active ingredients.

Zum Zwecke der Nachauflaufbehandlung wurden die Testpflanzen je nach Wuchs form erst bei einer Wuchshöhe von 3 bis 15 cm mit den in Wasser suspendierten oder emulgierten Wirkstoffen behandelt. Die Aufwandmenge für die Nachauflaufbehandlung betrug 0,03 kg/ha a.S.For the purpose of post-emergence treatment, the test plants were treated with the active ingredients suspended or emulsified in water only at a growth height of 3 to 15 cm, depending on the growth habit. The application rate for post-emergence treatment was 0.03 kg / ha as

Die Pflanzen wurden artenspezifisch bei Temperaturen von 10-25°C bzw. 20-35°C gehalten. Die Versuchsperiode erstreckte sich über 2 bis 4 Wochen. Während dieser Zeit wurden die Pflanzen gepflegt und ihre Reaktion auf die einzelnen Behandlungen wurde ausgewertet.The plants were kept at 10-25 ° C and 20-35 ° C depending on the species. The trial period lasted 2 to 4 weeks. During this time, the plants were cared for and their response to the individual treatments was evaluated.

Bewertet wurde nach einer Skala von 0 bis 100. Dabei bedeutet 100 kein Aufgang der Pflanzen bzw. völlige Zerstörung zumindest der oberirdischen Teile und 0 keine Schädigung oder normaler Wachstumsverlauf.Evaluation was carried out on a scale from 0 to 100. 100 means no emergence of the plants or complete destruction of at least the aerial parts and 0 means no damage or normal growth.

Die in den Gewächshausversuchen verwendeten Pflanzen setzten sich aus folgenden Arten zusammen: Lateinischer Name Deutscher Name Abutilon theophrasti Chinesischer Hanf Amaranthus retroflexus Zurückgekrümmter Fuchsschwanz Oryza sativa Reis Solanum nigrum Schwarzer Nachtschatten Ipomoea subspecies Prunkwindearten Triticum aestivum Sommerweizen The plants used in the greenhouse experiments are composed of the following types: Latin name German name Abutilon theophrasti Chinese hemp Amaranthus retroflexus Curved foxtail Oryza sativa rice Solanum nigrum Black nightshade Ipomoea subspecies Magnificent wind species Triticum aestivum Summer wheat

Mit 0,03 und 0,015 kg/ha a.S. im Nachauflaufverfahren eingesetzt, lassen sich mit dem Beispiel 2 breitblättrige unerwünschte Pflanzen sehr gut bekämpfen. Gleichzeitig ist die Verbindung 2 verträglich für die Kulturpflanzen Sommerweizen und Reis.With 0.03 and 0.015 kg / ha a.S. used in the post-emergence process, 2 broad-leaved unwanted plants can be combated very well with Example. At the same time, compound 2 is compatible with the summer wheat and rice crops.

Claims (6)

  1. A herbicide containing conventional inert additives and at least one styrene derivative of the formula I
    Figure imgb0044
     where R1 is hydrogen or halogen, R2 is halogen, R3 is hydrogen, halogen or C1-C4-alkyl, R4 is cyano or C1-C6-alkylcarbonyl and A is a heterocyclic radical selected from the groups A1 to A4
    Figure imgb0045
     where R5 and R6 are each hydrogen, methyl or ethyl, n is 0 or 1 and X is oxygen or sulfur, with the proviso that R2 is chlorine and R4 is C1-C6-alkylcarbonyl when A is A2, or an agriculturally useful salt of I.
  2. A process for the preparation of a styrene derivative of the formula I as claimed in claim 1, wherein a benzaldehyde derivative of the formula II
    Figure imgb0046
     is reacted with a phosphorane of the formula III
    Figure imgb0047
     where Ar is aryl.
  3. A method for controlling undesirable plant growth, wherein the undesirable plants and/or their habitat are or is treated with a herbicidal amount of a styrene derivative of the formula I as claimed in claim 1.
  4. A method for the defoliation of cotton, wherein the cotton plants are treated with an effective amount of a styrene derivative of the formula I as claimed in claim 1.
  5. Use of a styrene derivative of the formula I as claimed in claim 1 as a herbicide or bioregulator.
EP91121314A 1990-12-29 1991-12-12 Styrene derivatives Expired - Lifetime EP0493721B1 (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE4042194 1990-12-29
DE4042194A DE4042194A1 (en) 1990-12-29 1990-12-29 STYRENE DERIVATIVES

Publications (2)

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EP0493721A1 EP0493721A1 (en) 1992-07-08
EP0493721B1 true EP0493721B1 (en) 1997-05-14

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EP91121314A Expired - Lifetime EP0493721B1 (en) 1990-12-29 1991-12-12 Styrene derivatives

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US (1) US5356860A (en)
EP (1) EP0493721B1 (en)
JP (1) JPH04308568A (en)
KR (1) KR920012028A (en)
AT (1) ATE153017T1 (en)
CA (1) CA2058469A1 (en)
DE (2) DE4042194A1 (en)
HU (1) HU210729B (en)

Families Citing this family (2)

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Publication number Priority date Publication date Assignee Title
AU2274795A (en) * 1994-04-08 1995-10-30 Degussa A.G. Herbicidal bicyclic and tricyclic imides
DE4438578A1 (en) * 1994-10-28 1996-05-02 Basf Ag Substituted phthalimido-cinnamic acid derivatives and intermediates for their preparation

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE3724399A1 (en) * 1987-07-23 1989-02-02 Basf Ag PHENYL ALKENYLCARBONSAEURES AND THEIR ESTERS
DE3901705A1 (en) * 1989-01-21 1990-07-26 Basf Ag N-PHENYLTETRAHYDROINDAZOLE DERIVATIVES OF GENERAL FORMULAS IA AND IB

Family Cites Families (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE2714653C3 (en) * 1977-04-01 1980-10-30 Bayer Ag, 5090 Leverkusen Styryl cationic dyes and methods of dyeing with these dyes
JPS60194189A (en) * 1984-03-07 1985-10-02 三菱化学株式会社 Vinyl tricianide dye for alkali resist and discharge style
DE3603789A1 (en) * 1986-02-07 1987-08-13 Basf Ag N-SUBSTITUTED 3,4,5,6-TETRAHYDROPHTHALIMIDES
GB8620251D0 (en) * 1986-08-20 1986-10-01 Ici Plc Fungicides
US4914190A (en) * 1987-03-19 1990-04-03 Ciba-Geigy Corporation Tricyanovinyl-N,N-disubstituted anilines as disperse dyes
DE3714373A1 (en) * 1987-04-30 1988-11-10 Hoechst Ag SUBSTITUTED TETRAHYDROPHTHALIMIDES, METHOD FOR THE PRODUCTION THEREOF AND THEIR USE AS HERBICIDES
US4958043A (en) * 1988-04-18 1990-09-18 Eastman Kodak Company Novel methine compounds, polymers containing them and formed articles therefrom
DE3901550A1 (en) * 1989-01-20 1990-07-26 Basf Ag NEW TETRAHYDROINDAZOLE WITH PHENYL ETHER STRUCTURE
DE3917676A1 (en) * 1989-05-31 1990-12-06 Basf Ag 5-Tetra:hydro:phthalimido-cinnamic acid derivs.
DE3924719A1 (en) * 1989-07-26 1991-01-31 Basf Ag cinnamic

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE3724399A1 (en) * 1987-07-23 1989-02-02 Basf Ag PHENYL ALKENYLCARBONSAEURES AND THEIR ESTERS
DE3901705A1 (en) * 1989-01-21 1990-07-26 Basf Ag N-PHENYLTETRAHYDROINDAZOLE DERIVATIVES OF GENERAL FORMULAS IA AND IB

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JPH04308568A (en) 1992-10-30
DE59108703D1 (en) 1997-06-19
ATE153017T1 (en) 1997-05-15
HUT59561A (en) 1992-06-29
CA2058469A1 (en) 1992-06-30
EP0493721A1 (en) 1992-07-08
DE4042194A1 (en) 1992-07-02
KR920012028A (en) 1992-07-25
HU914126D0 (en) 1992-03-30
US5356860A (en) 1994-10-18
HU210729B (en) 1995-07-28

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